Water-soluble phthalocyanine dyestuffs



The present invention provides valuable phthalocyanine dyestulfs readilysoluble in water which correspond to the following formula:

in which Pc represents a metal-containing phthalocyanine nucleus, Xmeans a direct linkage or a bivalent organic radical, Y represents thegroup or the group -SO --CH=CH the radicals X and Y standing in Inetaorpara-position one to the other, 11 represents a whole number of 1 to 3and m likewise a whole number of 1 to 3, the sum of n and m being atmost 4, and wherein the benzene nucleus A may contain furthersubstituents.

As examples for a bivalent organic radical defined by X the followinggroupings may be named, for instance,

The novel dyestuffs, which possess valuable tinctorial properties, canbe prepared by condensing an amine of the general formula H2NX q inwhich X, Y and A have the meanings indicated above, with aphthalocyanine sulfonic acid chloride and, if desired, treating theproduct so obtained with an alkali.

The dyestuflYs of the invention can also be prepared by condensing anamine of the general formula HzN-X A l SOr-CHz-CHr-OH United StatesPatent O in which X and A have the meanings indicated above, with aphthalocyanine sulfonic acid chloride, converting the condensationproduct so obtained into the acid sulfuric acid ester and, if desired,treating the latter with an alkali.

The novel dyestuiis can be used for printing and dyeing processes. Theirspecial value resides in the fact that fibers of native or regeneratedcellulose can be dyed from salt-containing dye baths, either in the coldor in the hot, with the aid of alkalies, and blue to green dyeings areobtained which are distinguished by good wet fastness properties, a goodfastness to rubbing, a good to very good fastness to light and a highbrilliancy.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto, the parts being by weight unlessotherwise stated and the relationship of parts by weight to parts byvolume being the same as that of the kilogram to the liter.

Example I 60.3 parts of e-hydroxyethyl (3-amino )-phenylsulfone areconverted into the acid sulfuric acid ester by heating with 48.6 partsof sulfuric acid of 60% strength. The reaction product is poured on toice and the solution so obtained is neutralized by cautiously addingsodium hydroxide and sodium bicarbonate. Water is then added in anamount that the total volume is 1500 parts by volume. 97 parts ofcopper-phthalocyanine-(3)-tetrasulfochloride (obtainable as described inUS. Patent 2,219,330) and 50 parts of sodium bicarbonate are thenintroduced, 10 parts of pyridine are added and the mixture is stirred atroom temperature until the whole has been dissolved. The solution isthen heated for a further 30 minutes at 50 C. The dyestufi is isolatedby salting out with potassium chloride. After drying at 60 C. 250 partsof a blue product are obtained which dissolves in water with a turquoiseblue coloration. By the action of agents having an alkaline reaction thedyestuit can be fixed on cotton and yields turquoise blue dyeings andprints having a good fastness to washing and to light. It has thefollowing formula:

wherein Pc represents a copper-phthalocyanine nucleus, 11 represents awhole number of l to 3 and m likewise a whole number of 1 to 3, the sumof n and in being 4.

Dyestuffs having similar properties can be obtained by using in theabove example instead of fi-hydroxyethyl-(31 amino)-phenylsulfone thecorresponding amounts of the following amines containingfi-hydroxyethyl-sulfone groups:

B-hydroxyethyL (3 -amino-4-methoxy) -phenylsulfone, fl-hydroxyethyl-3-amino-4-methyl) phenylsulfone, fl-hydroxyethyl- 3-bron1o-4-amino-phenylsulfone, ,B-hydro xyethyl-( 3-amino-4-carboxy) -phenylsulfone orfl-hydroxyethyl- 3-amino-4-sulfo) -phenylsulfone Example 2 84.3 parts ofthe acid sulfuric acid ester of ,B-hydroxyethyl-(4-amino)'phenylsulfoneare dissolved in 700 parts of water by introducing dropwise 28.4 partsof sodium hydroxide solution of 33% strength and then adding solidsodium bicarbonate until the solution is neutral, the temperature beingkept below 10 C. 87.2 parts of copperphthalocyanine-(3)-trisulfochloride(obtainable as described in US. Patent 2,219,330) are introduced intothis solution, 10 parts of pyridine are added and the mixture is stirredat room temperature. By dropping in 2 N sodium hydroxide solution apH-value of 6.5 is maintained. As soon as the whole has been dissolvedand sodium hydroxide solution is no longer consumed, the mixture isheated for 1 hour at 4050 C. and the dyestuif is salted out withpotassium chloride. After drying, 190 parts of a turquoise blue dyestuffare obtained which can be fixed on cotton fibers with the aid of agentshaving an alkaline reaction and yields dyeings having a very goodfastness to washing and to light.

Example 3 A solution of 84.5 parts of the acid sulfuric acid ester ofB-hydroxyethyl-(4-amino)-phenylsulfone is prepared as described inExample 2, and into this solution 97 parts ofcopper-phthalocyanine-(4)-tetrasulfochloride (cf. US. Patent 2,219,330,Example 9) are introduced. 10 parts of pyridine are then added and themixture is stirred at 2030 C. until the whole has been dissolved. Bydropping in 2 N sodium hydroxide solution a pH-value of 66.5 ismaintained. The mixture is then heated for 1 hour at 40-50" C. andWorked up as described in Example 2. The dyestulf so obtained is veryreadily soluble in water and yields on cotton fibers with the aid ofagents having an alkaline reaction turquoise blue dyeings and printswhich possess good properties of fastness.

Example 4 97 parts of copper-phthalocyanine-(3)-tetrasulfochloride aresuspended in 1000 parts of ice-water. A solution of 100 parts of sodiumbicarbonate and 56.5 parts of the hydrochloride of B-hydroxyethyl[4-(B-aminoethyl)- phenyl]-su1fone of the formula in 1500 parts of Wateris added and the mixture is stirred for 12 hours at room temperature,for 1 hour at 40 C. and for 1 hour at 6070 C. 250 parts of potassiumchloride are then added and the condensation product is isolated bysuction-filtration. After drying the product so obtained is introducedat a temperature below 40 C. into 1000 parts of concentrated sulfuricacid and the mixture is stirred for 12 hours at room temperature. Thesolution obtained is then poured on a mixture of 2000 parts of asaturated potassium chloride solution and 2000 parts of ice, and afterhaving been stirred for a short while, the reaction product is filteredoff with suction. The residue is repeatedly washed with a potassiumchloride solution of 15% strength, then stirred with 2000 parts of Waterand 200 parts of anhydrous sodium acetate are added. The product isfiltered off with suction, repeatedly washed with a potassium chloridesolution of 15% strength and dried at 50-60 C.

135 parts of a blue powder are obtained which dissolves in water to givea turquoise blue colored solution. On cotton fibers the dyestuif yields,when developed with an alkaline agent, turquoise blue dyeings and printshaving good properties of fastness.

The hydrochloride of [B-hydroxyethyl-[4-(f3-aminoethyl)-phenyl]-sulfoneof the formula indicated above, which is used for the manufacture of theaforesaid dyestuff, can be prepared, for example in the followingmanner:

N-acetyl-fi-phenylethylamine is converted into 4-[( 3-acetylamino)-ethyl]-benzene-sulfochloride by treating it withchlorosulfonic acid. By reduction of the sulfochloride with sodiumsulfite the corresponding sulfinic acid is obtained which is reactedwith fi-chloroethanol or ethylene oxide to form the,B-hydroxyethyl-[4-(fi-acetamine-ethyl)-phenyl]-sulfone having a meltingpoint of 102-103 C. By saponification with hydrochloric acid thehydrochloride of the fi-hydroxyethyl-[4-(f3-aminoethyl)-phenyl]-sulfoneis obtained in the form of white needles having a melting point of 100C. The product contains 1 mol of crystal Water.

4 Example 5 29 parts ofB-hydroxyethyl-[3-nitro-4-(fl-aminoethylamino)-phenyl]-sulfone of theformula are suspended in 1000 parts of ice-water. 50 parts of sodiumbicarbonate are added and, while cooling with ice, 48.5 parts ofcopper-phthalocyanine-(3)-tetrasulfochloride are introduced. The mixtureis stirred for 2 hours while cooling with ice and then stirred overnightat room temperature. The mixture is then heated for 1 hour at 4050 C.and for another hour at 60-70 C., 150 parts of potassium chloride areadded, the whole is allowed to cool and the condensation product isisolated by suction filtration. After drying the product is esterifiedas described in Example 4 with 500 parts of concentrated sulfuric acid.The ester dyestulf is obtained in the form of a dark green powder. Bythe action of alkalies the dyestulf can be fixed on cotton, bluish greendyeings and prints having good properties of fastness being obtained.

The B-hydroxyethyl-[3-nitro-4-(fi-aminoethyl-amino)- phenyl]-sulfone ofthe above formula used for the manufacture of the said dyestuif can beprepared, for example, as follows:

20 parts of copper-II-chloride are introduced into 440 parts of ethylenediamine of 78% strength and 265 parts of fl-hydroxyethyl-[(3-nitro-4-chloro)-phenyl] -sulfone are then added slowly, while thetemperature is maintained below 70 C. by external cooling. The mixtureis stirred for minutes at 80-90 C. and then cooled, poured into 1000parts of ice-water, stirred for 30 minutes, while cooling, and filteredoff with suction. The residue is washed with water and recrystallizedfrom alcohol. 227 parts of ,B-hydroxyethyl [3-nitro4-(fl-amino-ethylamino)- phenylJ-sulfone are obtained in the form ofyellow crystals having a melting point of 151-152 C.

A dyestuff of similar properties is obtained when the p-hydroxyethyl- [3-nitro-4- (B-aminoethyl-amino -phenyl] sulfone is replaced by 33.7 partsof B-hydroxyethyl-[3- nitro-4-(4'-arninophenyl-amino)-phenyl]-sulfone ofthe formula which can be prepared by reacting fi-hydroxyethyl-[(3-nitro-4-chloro)-phenyl] -sulfone with 4-amino-acetanilide andsubsequently saponifying the product so obtained.

Example 6 35 parts of sodium bicarbonate are added to neutralizedsolution of 43.5 parts of the acid sulfuric acid ester offl-hydroxyethyl-(4-amino)-phenylsulfone in 400 parts of water and 48.5parts of nickel-phthalocyanine-(3)- tetrasulfochloride are introduced. 5parts of pyridine are then added and the mixture is stirred for 48 hoursat room temperature. The whole is heated for 1 hour at 50 C., thesolution obtained is clarified by suction-filtration and the dyestuff issalted out With potassium chloride. After drying, 65 parts of a greenblue powder are obtained.

The dyestuff is readily soluble in water and can be fixed with alkalieson fibers of native or regenerated cellulose to yield dyeings which arefast to washing and to light.

Example 7 80.4 parts of fi-hydroxyethyl-(4-arnino)-phenylsu1fone areconverted by heating with 64.8 parts of sulfuric acid of 60% strengthinto the acid sulfuric acid ester, then stirred with 600 parts of Water,mixed at 810 C. with 36.7 parts of sodium hydroxide solution of 33 B.and rendered neutral to delta-paper by the addition of 12 parts ofsodium bicarbonate. parts ofcopper-phthalocyanine-(3)-tetrasulfochloride of 100% strength areintroduced into this solution in the form of a moist paste, and thecondensation is carried out at a pH-value of 6-6.5, while stirring at-25 C., by adding sodium hydroxide solution and a small amount ofpyridine. When the condensation is complete, the solution is mixed withsodium hydroxide solution of 33 B. until a pH-value of 12 is attained,the dyestulf is then salted out by the addition of potassium chloride,filtered off with suction and dried. It is a blue powder which dissolvesin water to give a blue color solution. From salt-containing dye bathsthere are obtained with the aid of alkalies on fibers of native andregenerated cellulose clear turquoise blue dyeings which possess goodWet fastness properties, a good fastness to rubbing and a good to verygood fastness to light.

Example 8 50 parts offi-hydroxyethyl-[3-(4'-amin0-benzoylamino)-4-hydroxyphenyl]-sulfone ofthe formula are introduced at a temperature below C. into 200 parts ofconcentrated sulfuric acid and stirred for 4 hours at 40 C. The solutionis then poured on ice, the precipitated sulfuric acid ester is filteredoff with suction and washed with a small amount of water. The filterresidue is dissolved in water with the addition of sodium bicarbonate,the solution is neutralized and 48.5 parts of copper-phthalocyanine-( 3)-tetrasulfochloride are introduced. 5 parts of pyridine are then addedto the mixture and the whole is stirred at room temperature, the neutralreaction being maintained by adding dropwise 2 N sodium hydroxidesolution. When sodium hydroxide solution is no longer consumed, theproduct is isolated in the usual manner. A turquoise blue dyestutf isobtained which yields on cotton by the action of agents having alkalinereaction, dyeings which are fast to washing and to light.

The [i hydroxyethyl [3 (4 amino-benzoylamino)- 4-hydroxyphenyl1-sulfoneof the above formula, which is used for the manufacture of the saiddyestuff, can be prepared by reacting [3 hydroxyethyl (3 amino 4-hydroxy)-phenyl-sulfone with 4-nitrobenzoyl chloride and subsequentlyreducing the product so obtained.

We claim:

1. A water-soluble phthalocyanine dyestuif of the formula wherein Pc ismetal phthalocyanine, X represents a member selected from the groupconsisting of p means an integer of 0 and 1, Y represents a memberselected from the group consisting of SO CH -CH OSO H and SO -CH=CH Xstanding in one of the positions meta and para to Y, Z represents amember selected from the group consisting of hydrogen, bromine, methyl,methoxy, nitro, hydroxl, carboxy and sulfo, n represents a whole numberof 1 to 3 and m likewise a whole number of 1 to 3, the sum of n and mbeing at most 4.

2. A water-soluble phthalocyanine-dyestuff of the formula wherein Pcstands for nickel phthalocyanine or copper phthalocyanine, X representsa member selected from the group consisting of -CH CH p means an integerof 0 and 1, X standing in one of the positions meta and para to thegroup Z represents a member selected from the group consisting ofhydrogen, bromine, methyl, methoxy, nitro, hydroxyl, carboxy and sulfo,n represents a whole number of 1 to 3 and m likewise a whole number of 1to 3, the sum of n and in being at most 4.

3. The water-soluble phthalocyanine-dyestuff of the formula wherein Feis copper phthalocyanine, n represents a whole number of 1 and 2, and mlikewise a whole number of 1 and 2, the sum of n and m being 3.

4. The water-soluble phthalocyanine-dyestui'f of the wherein Fe iscopper phthalocyanine, n represents a whole number of 1 to 3 and mlikewise a whole number of 1 to 3, the sum of n and in being 4.

5. The Water-soluble phthalocyanine-dyestuff of the formula wherein P0is copper phthalocyanine, n represents a whole number of 1 to 3 and mlikewise a whole number of 1 to 3, the sum of n and m being 4.

7. The water-soluble phthalocyanine-dyestutf of the formulaSOrCHrCHrOSOaH 7 8 wherein P0 is copper phthalocyanine, n represents aReferences Cited by the Examiner Whole number Of 1 t0 3 and m likewise a'WhOle nurn- UNITED STATES PATENTS 'ber of 1 to 3, the sum of n and inbeing 4.

h ff h 2,657,205 10/1953 Heyna et a1. 260-3145 fofml'llige Water solublepht alocyanlne yestu of t e 5 2,670,265 2/1954 Heyna et a1. 260 314'52,935,506 5/1960 Heslop et a1. 260314.5 3,046,075 7/ 1962 Kantner et a1260314.5 /[SO3H]n 3,062,830 11/1962 Buc et a1. 260-314.5 et OTHERREFERENCES SOTNH SOTOHZ CHZ OSOBHL 10 Wegmann, Textil-Praxis (Oct.1958), pages 1056-1061.

h k 1 h h h 1 WALTER A. MODANCE, Primary Examiner. w erein Fe is nic e pt alocyanine, n represents a W o e number of 1 and 2 and m likewise awhole number of IRVING MARCUS JOHN RANDOLPH Examiners 1 and 2 the sum ofn and m being 3 15 I. A. PATTEN, Assistant Examiner.

1. A WATER-SOLUBLE PHTHALOCYANINE DYESTUFF OF THE FORMULA